Dye composition for keratin fibres comprising a specific direct dye

ABSTRACT

The invention relates to a dye composition, in particular a lightening dye composition, for keratin fibers, in particular for human keratin fibers such as the hair, comprising, in a medium which is suitable for dyeing, at least one direct dye to be mixed at the time of use, at basic pH, with an oxidizing agent, and characterized in that it has a basic pH and in that it contains, as direct dye, at least one dye containing an optionally delocalizable quaternized nitrogen atom and a —Z═N— bond in which Z denotes a nitrogen atom or a —CH— radical.  
     The invention also relates to the use of the composition and the multi-compartment dyeing devices, for the dyeing of keratin fibers, in particular the hair.

[0001] The present invention relates to a dye composition, in particulara lightening dye composition, for keratin fibers, and in particularhuman keratin fibers, comprising at least one direct dye chosen from thegroup formed by dyes containing an optionally delocalizable quaternizednitrogen atom and a —Z═N— bond, in which Z denotes a nitrogen atom or a—CH— radical. The invention also relates to the use of such acomposition in the above-mentioned application.

[0002] It is known to dye keratin fibers, and in particular human hair,with dye compositions containing direct dyes according to a so-called“direct dyeing” process. This process involves applying to the keratinfibers dye molecules that have an affinity for the fibers, leaving thefibres to stand, and then rinsing the fibers. This process allowsshading of the color of the keratin fibers to be obtained. It is alsoknown to dye keratin fibers, and in particular human hair, with dyecompositions containing oxidation dye precursors (ortho- orpara-phenylenediamines and ortho- or para-aminophenols, generallyreferred to as “oxidation bases”) and couplers (meta-phenylenediamines,meta-aminophenols and meta-diphenols, also referred to as colormodifiers, which allow the “base” colors obtained by the condensationproducts of the oxidation bases to be modified and enriched withglints), according to a so-called “oxidation dyeing” process.

[0003] The oxidation dyeing process usually involves lightening, that isto say that it involves applying to the keratin fibers, at basic pH, amixture of bases and couplers and aqueous hydrogen peroxide solution,leaving the applied mixture to stand on the hair and then rinsing thehair. It allows, particularly in the case of hair dyeing, the melanin tobe lightened and the hair to be dyed.

[0004] Lightening the melanin has the advantageous effect of creating aunified coloration in the case of grey hair, and, in the case ofnaturally pigmented hair, of bringing out the color, that is to say ofmaking it more visible.

[0005] An oxidizing agent and, in particular, an aqueous hydrogenperoxide solution, and a basifying agent are used to obtain thislightening. A lightening of the melanin ranging from ¾ of a tone to morethan 2 tones can be brought about as a function of the concentrations ofaqueous hydrogen peroxide and of basifying agent, and also as a functionof the nature of the basifying agent. In the case of gentle lightenings,the desired lightening is obtained in the course of superpositions.

[0006] In the so-called oxidation dyeing of hair, the use of oxidationbases sometimes leads to problems of sensitization of the scalp. In thiscase, if it is nevertheless desired to dye the hair, it is then possibleonly to use direct dyeing, with its drawbacks, in particular that of nolonger obtaining the tinting effects of oxidation dyeing sinceconventional direct dyeing is, by itself, not lightening.

[0007] It has already been attempted in the past to obtain lighteningdyes, by replacing the oxidation bases and the couplers with directdyes. However, all the results obtained were less than optimal.

[0008] Accordingly, it was proposed to dye the hair with dyecompositions based on nitro direct dyes and/or dispersed azo dyes andammoniacal aqueous hydrogen peroxide (see in this respect French patentno. FR-1,584,965 and Japanese patent no. JP-062,711,435) by applying tothe hair a mixture of the dyes and the oxidizing agent, which isprepared just before use. However, the colorations obtained did notprove to be sufficiently fast and disappeared on shampooing, allowingthe lightening of the hair fibre to emerge. Such a coloration becomesaesthetically unpleasant by changing over time.

[0009] It has also been proposed to dye the hair with compositions basedon cationic direct dyes of oxazine type and ammoniacal aqueous hydrogenperoxide (see in this respect Japanese patents JP-53 95693 and JP-55022638) by applying to the hair, in a first step, ammoniacal aqueoushydrogen peroxide, and then, in a second step, a composition based onthe oxazine direct dye. The coloration obtained is not satisfactory, onaccount of the fact that it requires a process which is made too slow bythe standing times of the two successive steps. If, moreover, a mixture,prepared at the time of use, of the oxazine direct dye with ammoniacalaqueous hydrogen peroxide is applied to the hair, the hair fibre is notdyed or, at best, a coloration which is virtually nonexistent isobtained.

[0010] Moreover, the Inventor has performed tests to dye the hair withdye compositions based on anionic sulfonic dyes (which are themselvesreputed for the excellent fastness) and on ammoniacal aqueous hydrogenperoxide, by applying to the hair a mixture of the dyes and theoxidizing agent, which is prepared just before use. However, in thiscase, no coloration of the hair fibre was observed.

[0011] Now, after considerable research has been conducted in thisdirection, the Inventor has discovered that it is possible to obtaindyes, in particular lightening dyes, with specific and suitably selecteddirect dyes, which are fast, homogenous and do not change on washing, byusing a mixture which is prepared at the time of use, at basic pH, of anoxidizing agent and at least one direct dye which is chosen from thosecontaining both an optionally delocalizable quaternized nitrogen atomand a —Z═N— bond, in which Z denotes a nitrogen atom or a —CH— radical.This discovery forms the basis of the present invention.

[0012] One subject of the present invention is thus a dye composition,in particular a lightening dye composition, for keratin fibers, and inparticular for human keratin fibers such as the hair, of the typecomprising, in a medium which is suitable for dyeing, at least onedirect dye to be mixed at the time or use, at basic pH, with anoxidizing composition, and which is characterized in that it has a basicpH and in that it contains, as the direct dye, at least one dyecontaining an optionally delocalizable quaternized nitrogen atom and a—Z═N— bond in which Z denotes a nitrogen atom or a —CH— radical.

[0013] The dyes used in accordance with the present invention make itpossible to achieve homogenous and fast colorations which remainaesthetic over time, since they do not change either over time or onwashing. They are furthermore produced very rapidly, and in particularin a standing time of the dye/oxidizing agent mixture of five minutes.In addition, they communicate an especially shiny appearance and anatural feel without overloading, in particular on hair fibers.

[0014] Another subject of the present invention relates to a process fordyeing, and in particular lightening, keratin fibers, in particularhuman keratin fibers such as the hair, which involves applying to thosefibers at least one composition (A) containing, in a medium which issuitable for dyeing, at least one direct dye containing an optionallydelocalizable quaternized nitrogen atom and a —Z═N— bond in which Zdenotes a nitrogen atom or a —CH— radical, the lightening being ensured,at basic pH, using an oxidizing agent which is mixed with thecomposition (A) just prior to use, or which is present in a separatecomposition (B) that is applied simultaneously.

[0015] Another subject of the invention is multi-compartment dyeingdevices or “kits”, the first compartment of which contains at least onedirect dye containing an optionally delocalizable quaternized nitrogenatom and a —Z═N— bond in which Z denotes a nitrogen atom or a —CH—radical, as well as a basifying agent, and the second compartment ofwhich contains an oxidizing agent. Another alternative “kit” is composedof a first compartment containing at least one direct dye as mentionedabove, a second compartment containing a basifying agent and a thirdcompartment containing an oxidizing agent.

[0016] The invention also relates to a “ready-to-use composition”,characterized in that it contains, in a medium which is suitable fordyeing, at least one direct dye containing an optionally delocalizablequaternized nitrogen atom and a —Z═N— bond, in which Z denotes anitrogen atom or a —CH— radical, an oxidizing agent and also, ifnecessary, a basifying agent in an amount which is sufficient to adjustthe final pH to a value above 7, and preferably to a value ranging from8.5 to 11.

[0017] However, other characteristics, aspects, subjects and advantagesof the invention will emerge even more clearly on reading thedescription and the examples which follow.

[0018] The direct dyes containing an optionally delocalizablequaternized nitrogen atom and a —Z═N— bond, in which Z denotes anitrogen atom or a —CH— radical, which may be used according to theinvention are preferably chosen from the compounds of formula (I) below:

[0019] in which Z denotes a nitrogen atom or a —CH— radical. A and Beach independently denote an optionally substituted benzenic orheterocyclic aromatic group, wherein each of the aromatic groups isoptionally substituted on any ring atom, including the ring atom boundto the Z or N moiety of formula (I). The aromatic groups are preferablysubstituted with one or more halogen atoms or with one or more radicalssuch as a methyl radical, a phenyl radical, an NR₁R₂ radical or an OR₁radical, in which R₁ and R₂, simultaneously or independently of eachother, represent hydrogen, a C₁-C₈ alkyl radical, a C₁-C₈ hydroxyalkylradical or a phenyl radical. X denotes an anion, preferably chloride ormethyl sulphate, it being possible for the cationic charge to form anintegral part of the aromatic ring or to be carried by one of itssubstituents.

[0020] These dyes are well known in the prior art and are described inpatent applications WO-95/01772 and WO-95/15144, the disclosures ofwhich are incorporated herein by reference.

[0021] Among the compounds of formula (I) which can be used in thecontext of the present invention, and whose cationic charge is carriedby a substituent on one of the aromatic rings, it is preferred to usethe compounds of the following formulae:

[0022] i.e., 4-aminophenylazo-2-hydroxy-8-trimethylammonio-naphthalonechloride;

[0023] i.e., 2-methoxyphenylaze-2-hydroxy-8-trimethylammonionaphthalenechloride;

[0024] i.e.,4-amino-3-nitrophenylazo-2-hydroxy-8-trimethylammonio-naphthalenechloride; and

[0025] i.e.,8-trimethylammoniophenylazo-N-phenyl-3methyl-5-hydroxy-pyridazinechloride.

[0026] According to the present invention, it is even more preferred touse compounds of formula (I) whose cationic charge forms an integralpart of one of the aromatic rings. Among the compounds that may bementioned, by way of non-limiting examples, are the compounds of thefollowing formulae:

[0027] i.e., (1-methyl-1-phenyl)-2 (1-methine-4N-methylpyrdinylium]hydrazine chloride;

[0028] i.e.(1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N-methylpyridinylium)hydrazine chloride;

[0029] i.e.(1-methyl-1-paramethoxyphenyl)-2-(1-methine-4N-methylpyridinylium)hydrazine methylsulphate;

[0030] i.e., 4-dimethylaminophenylazo-2N-methyl-5N-methyl-imidazolyliumchloride

[0031] i.e., 4-dimethylaminophenylazo-2N-methyl-3N-methyl-imidazolyiumchloride;

[0032] i.e., 1-methylaminophenylazo-2N-methyl-5N-methyl-imidazolyliumchloride;

[0033] i.e., 4-aminophenylaze-2N-methyl-5N-methylimidazolylium chloride;

[0034] i.e., 4-dimethylaminophenylazo-4N-methyl-pyridinylium chloride;and

[0035] i.e., 4-dimethylaminophenylazo-4N-oxido-pyridinylium chloride.

[0036] The concentration of direct dye(s) of formula (I) preferablyranges from 0.001 to 5% by weight approximately relative to the totalweight of the dye composition before it is mixed with the oxidizingagent, and more preferably ranges from approximately 0.05 to 2%.

[0037] The oxidizing agent is preferably chosen from hydrogen peroxide,urea peroxide, alkali metal bromates and persalts such as perborates andpersulphates. The use of hydrogen peroxide is particularly preferred.

[0038] The pH of composition (A) which contains at least one direct dyeof formula (I) as well as that of composition (B) containing theoxidizing agent as defined above are such that after mixing composition(A) with composition (B), the pH of the composition applied to the humankeratin fibers is preferably above 7, and more preferably ranges from8.5 to 11. The pH is preferably adjusted to the chosen value usingbasifying agents, or possibly acidifying agents, which are well known inthe state of the art in the dyeing of keratin fibers.

[0039] Basifying agents which may be mentioned are aqueous ammonia,alkaline carbonates, alkanolamines, for example mono-, di- andtriethanolamines and derivatives thereof, sodium hydroxide, potassiumhydroxide and compounds of formula (II):

[0040] in which R is a propylene residue optionally substituted with ahydroxyl group of a C₁-C₄ alkyl radical, R₃, R₄, R₅, and R₆,simultaneously or independently of each other, represent a hydrogenatom, a C₁-C₄ alkyl radical or a C₁-C₄ hydroxyalkyl radical.

[0041] The acidifying agents are conventionally inorganic acids such as,for example, hydrochloric acid, tartaric acid, citric acid andphosphoric acid.

[0042] The oxidizing composition (B) preferably comprises an aqueoushydrogen peroxide solution whose titre may range, more particularly,from 5 to 40 volumes approximately.

[0043] The basifying agent is preferably chosen from alkanolamines whenmoderate lightening is required, and it is more particularly representedby aqueous ammonia when more pronounced lightening is desired.

[0044] The medium suitable for dyeing is preferably an aqueous mediumcomprising water and more-preferably a water/solvent(s) mixture, thesolvent(s) being chosen from organic solvents such as 2-butoxyethanol orethanol.

[0045] According to a preferred embodiment of the dyeing process of theinvention, the dye composition (A) described above containing abasifying agent, and more particularly an aqueous solution of ammonia orof alkanolamine described above, is mixed, at the time of use, with anoxidizing solution in an amount which is sufficient to give rise tolightening of the melanin. The mixture obtained is then applied to humankeratin fibers and is left standing on them preferably for 1 to 45minutes, more preferably for 4 to 20 minutes, after which the fibers arerinsed, optionally washed with shampoo, rinsed again and dried.

[0046] The dye compositions according to the invention also contain, intheir preferred embodiments, surfactants which are well known in theart, in proportions ranging from approximately 0.5 to 55% by weight, andpreferably from 2 to 50% by weight relative to the total weight of thecomposition, organic solvents, in proportions ranging from approximately1 to 40% by weight, and in particular from 5 to 30% by weight relativeto the total weight of the composition, or any other cosmeticallyacceptable adjuvant known in the prior art in the oxidation dyeing ofhair.

[0047] The composition applied to the hair may be in various forms, suchas in liquid, cream or gel form, or in any other form which is suitablefor dyeing keratin fibers, and in particular human hair. In particular,it may be packaged under pressure in an aerosol can in the presence of apropellant and may form a foam.

[0048] Concrete examples illustrating the invention will now be given.These examples are not intended to limit the subject matter of theinvention.

EXAMPLES

[0049] EXAMPLE 1:

[0050] 0.5% by weight of each of the following seven direct dyes wasintroduced into 10% by weight of a 20% aqueous ammonia solution,followed by addition of 100% by weight of 20-volumes aqueous hydrogenperoxide.

[0051] Each of the seven compositions obtained above was then applied tolocks of European, non-permanent-waved hair containing 90% white hairs,and the compositions were allowed to remain on the hair for 30 minutes.After rinsing the locks with running water, followed by drying, thecoloration obtained was graded on a scale from 0 to 3, as follows:

[0052] Grade 0 - no coloration

[0053] Grade 1 - slightly perceptible but unacceptable coloration

[0054] Grade 2 - clearly perceptible coloration but at the limit ofacceptability

[0055] Grade 3 - good coloration.

[0056] The results obtained were as follows:

[0057] Dyes not according to the invention:

[0058] anionic sulfonic dye:

[0059] Acid Black 1 (C.l.20470)→grade=0

[0060] nitrobenzene dye:

[0061] N1, N4, N4-tris(β-hydroxyethyl)-1,4-diamino2-nitrobenzene→grade=1

[0062] cationic dye of oxazine type:

[0063] Basic Blue 3→grade=0

[0064] cationic dye containing no —N═N or —CH═N— function:

[0065] 1-(N-methylmorpholiniumpropylamino)-4-hydroxyanthraquinone(methyl sulphate)→grade=0

[0066] Dyes according to the invention (the Nos. correspond to theproducts in the description):

[0067] dye (8) with an —N═N— function→grade=3

[0068] dye (6) with a —CH═N— function→grade=3

[0069] Consequently, among the seven direct dyes studied, only the dyesaccording to the invention make it possible to obtain good lighteningcolorations.

[0070] EXAMPLE 2:

[0071] The following dye compositions were prepared:

[0072] Direct dye of formula (I) according to the invention* . . . ×g

[0073] 20% aqueous ammonia solution . . . 10 g

[0074] Demineralized water . . . g.s. for 100 g * See Table (I)following page, the Nos. corresponding to the products in thedescription.

[0075] In a first experiment (lightening dye according to theinvention), locks of natural chestnut brown European hair were dyed witha mixture, prepared at the time of use, of the composition describedabove with its weight of 20-volumes aqueous hydrogen peroxide. Afterallowing the composition to remain on the locks for 5 minutes, they wererinsed with running water and then dried.

[0076] In a second experiment (comparative standard direct dyeing),other locks of hair (same quality as above) were separately dyed with acomposition as described above, the only difference being that itcontained no aqueous hydrogen peroxide. After allowing the compositionto remain on the locks for the same length of time as for the abovedyeing, they were rinsed and then dried.

[0077] The lightening dyes according to the invention were thus comparedwith corresponding standard direct dyes, this being with the direct dyes(8), (10) and (10)÷(7) of formula (I) according to the invention.

[0078] The compared shades were measured in terms of L, a, b values(color notation system in which (L) denotes the intensity, (a) denotesthe shade and (b) denotes the purity) on a Minolta CM2002 colorimeter.TABLE (I) Dyeing with dye No. L, a, b L a b Comments (8): 2 g invention22.44 6.30 1.52 a increases → redder shade comparative 22.31 3.88 0.68(10): 0.4 g ÷ invention 23.74 5.35 3.96 a and b increase → (7): 1.8 gmore orange shade comparative 22.63 2.39 1.90 (10): 2 g invention 22.606.67 2.53 a increases → redder shade comparative 22.21 3.83 1.33 control22.62 1.84 2.06 (no dye)

[0079] These results demonstrate that the lightening dyeing using thedirect dyes according to the invention (with aqueous hydrogen peroxide)had better performance in terms of visual effect (generated more visiblecolorations) than standard direct dyeing with these same dyes (withoutaqueous hydrogen peroxide).

[0080] These lightening dyeings gave colorations that were moreoverhomogeneous, fast and shiny and which remained aesthetically attractiveover time. The hair also offered a natural appearance withoutoverloading.

I claim:
 1. A method for dyeing a keratin fibre, comprising the step ofapplying to said fibre a dye composition in an amount sufficient to dyesaid fibre, wherein said dye composition comprises, in a medium suitablefor dyeing, at least one direct dye containing an optionallydelocalizable quaternized nitrogen atom and a —Z═N— bond, in which Zdenotes a nitrogen atom or a —CH— radical, and at least one basifyingagent in an amount sufficient to render basic the pH of saidcomposition, while simultaneously applying to said fibre at least oneoxidizing agent whereby said at least one oxidizing agent is mixed withsaid dye composition.
 2. A method according to claim 1 , wherein saiddye composition comprises said at least one oxidizing agent.
 3. A methodaccording to claim 1 , wherein said at least one oxidizing agent ispresent in a composition separate from said dye composition.
 4. A methodaccording to claim 1 , wherein said at least one direct dye is acompound of formula (I):

in which Z denotes a nitrogen atom or a —CH— radical, A and B eachindependently denote an optionally substituted benzenic or heterocyclicaromatic group, and X⁻ denotes an anion, and wherein the cationic chargeforms an integral part of one of said aromatic groups or is carried byone of the substituents on said aromatic groups.
 5. A method accordingto claim 4 , wherein at least one of said one aromatic groups issubstituted by at least one substituent selected from halogen atoms,methyl radicals, phenyl radicals NR₁R₂ radicals and OR₁ radicals, inwhich R₁ and R₂ each independently represent hydrogen, a C₁-C₈ alkylradical, a C₁-C₄ hydroxyalkyl radical or a phenyl radical.
 6. A methodaccording to claim 4 , wherein X⁻ denotes a chloride or methyl sulphateanion.
 7. A method according to claim 4 , wherein said at least onedirect dye is selected from compounds of formula (I) wherein thecationic charge forms an integral part of one of said aromatic groups.8. A method according to claim 4 , wherein said at least one direct dyeis selected from compounds of formula (I) wherein the cationic charge iscarried by one of the substituents on said aromatic groups.
 9. A methodaccording to claim 1 , wherein said at least one direct dye is selectedfrom:


10. A method according to claim 1 , wherein said at least one direct dyeis present in a concentration ranging from 0.001 to 5% by weightrelative to the total weight of said dye composition before it is mixedwith said at least one oxidizing agent.
 11. A method according to claim10 , wherein said at least one direct dye is present in concentrationranging from 0.05 to 2% by weight relative to the total weight of saiddye composition before it is mixed with said at least one oxidizingagent.
 12. A method according to claim 1 , wherein said at least onebasifying agent is selected from aqueous ammonia and an alkanolamine.13. A method according to claim 1 , wherein said at least one basifyingagent is present in an amount sufficient to adjust the pH of the mixtureof said dye composition and said at least one oxidizing agent to a valueranging from 8.5 to
 11. 14. A method according to claim 1 , wherein saidat least one oxidizing agent comprises aqueous hydrogen peroxide.
 15. Amethod according to claim 1 , wherein said keratin fibre is a humankeratin fibre.
 16. A ready to-use dye composition, comprising, in amedium suitable for dyeing, (1) at least one direct dye containing anoptionally delocalizable quaternized nitrogen atom and a —Z═N— bond,wherein Z denotes a nitrogen atom or a —CH— radical, (2) at least onebasifying agent in an amount sufficient to render basic the pH of saiddye composition, and (3) at least one oxidizing agent.
 17. A compositionaccording to claim 16 , wherein said at least one basifying agent ispresent in an amount sufficient to adjust the pH of said dye compositionto a value ranging from 8.5 to
 11. 18. A composition according to claim16 , wherein said at least one oxidizing agent comprises aqueoushydrogen peroxide.
 19. A multi-compartment device or “kit” for thedyeing of a human keratin fibre, comprising at least two compartments,wherein one of said at least two compartments contains a dye compositioncomprising, in a medium suitable for dyeing, at least one direct dyecontaining an optionally delocalizable quaternized nitrogen atom and a—Z═N— bond, wherein Z denotes a nitrogen atom or a —CH— radical, andwherein another of said at least two compartments contains a compositioncomprising at least one oxidizing agent in a medium suitable for dyeing,and further wherein at least one basifying agent is present in a thirdcompartment of said device or in the compartment containing said dyecomposition.
 20. A method according to claim 1 , further comprisingallowing the mixture of said dye composition and said at least oneoxidizing agent to remain on said fibre for a time sufficient to dyesaid fibre, and subsequently rinsing said fibre.
 21. A method accordingto claim 20 , wherein said time ranges from 1 to 45 minutes.
 22. Amethod according to claim 21 , wherein said time ranges from 4 to 20minutes.
 23. A method according to claim 1 , wherein said dyecomposition is a lightening dye composition.
 24. A composition accordingto claim 16 , wherein said dye composition is a lightening dyecomposition.